Applications of density functional theory methods in millimeter‐wave spectroscopy

Density functional theory (DFT), using the most common functionals, and ab initio quantum chemistry methods are used to calculate the rotational constants and dipole moments of the astrophysically important molecules HCN, CH₃CN, CH₃CNH⁺, HCCCN, and HCCNC. As far as millimeter‐wave spectroscopy is of interest the DFT methods performed well with most functionals, giving results within ±1% of experiments for rotational constants and ±3% for dipole moments. Analyzing the results obtained with all theoretical models, it may be concluded that the Becke's three‐parameter exchange functional and the gradient‐corrected functional of Lee, Yang, and Paar (B3LYP) and Becke's three‐parameter functional with Perdew–Wang correlational functional [B3PW91/6‐31G(d, p)] give the best performances. A detailed analysis of the electron correlation effects shows that HCCCN is more stable than is HCCNC, by 1.16 eV, with important contribution arising from triple excitations. This result is also compared with those obtained with DFT methods. Despite occasional difficulties, DFT with the currently available functionals are of great utility in quickly assessing spectroscopic parameters of astrophysical interest. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2003     

Gelation of poly(n-butylisocyanate) in benzene

Poly (n-butylisocyanate)-benzene solutions prepared by solubilization at 45°C, followed by aging at room temperature were found to be metastable for months, although, eventually, they separated into a birefringent polymer-rich phase and an isotropic solution. These metastable solutions, as well as isothermally phase-separated biphasic samples, flowed and exhibited dynamic moduli indicative of low polymer connectivity. By contrast samples prepared by a freeze-thaw cycle were uniformly and highly birefringent and showed network (gel) behavior at room temperature. The mechanism of gel formation is most likely the exclusion of the polymer from the benzene crystal during crystallization, forcing the polymer to align and exist at grain boundaries. Films formed from solutions have different moduli than those formed from gels, and are consistent with the proposed mechanism.     

Scaling probability, key to the equilibrium statistical volume distribution in foams

The equilibrium statistical volume distribution in foams, which has been previously demonstrated to be the so-called log-normal, is accounted on probability grounds by a scaling law on the bubble's volume time-evolution. This law states that the conditional probability for a given bubble to have the volume v(t + Δt), he assumption that it was v(t), to depend solely on the relationship v(t + Δt)/v(t), and in particular, to be independent of the time t. The theoretical results, however, allow to go further. Indeed, since the time dependece of its parameters (expectation and variance) are given functions of time, only two parameters are necessary to describe completely the foam.     

Maximum Principles for Infinite Dimensional Diffusion Equations

In this paper we prove the validity of the Maximum Principle for some class of elliptic and parabolic equations of diffusion type in infinite dimension. The main tools are Asplund’s theorem and Preiss’ theorem on differentiability of Lipschitz functions in Banach space.      

Elastic instability of the nano-structured state as an intrinsic probe to study the early formation stages of sol–gel derived (Pb<Subscript>1-x</Subscript>Ca<Subscript>x</Subscript>)TiO<Subscript>3</Subscript> thin films

A novel method to investigate the early formation stages of polycrystalline (Pb_1-xCa_x)TiO₃ (PCT) perovskite films by means of traditional Brillouin and micro-Brillouin spectroscopy (BS, mBS) is described in the present work. The films were prepared by chemical solution deposition (CSD) onto oxidized (100)Si substrates and treated at temperatures between 350–650 °C by rapid thermal processing (RTP). The elastic instability observed by Brillouin spectroscopy at the nano-structured state of the PCT films was used here to determine their crystallization temperatures. Coexistence of different nanocrystalline phases (e.g., pyrochlore, perovskite) in the films could also be detected by this technique. The reliability of these results is demonstrated by complementary information obtained by X-ray diffraction (XRD) and scanning force microscopy (SFM). The effects of the annealing temperature and of the Ca²⁺ content on the crystallization process of these films are also discussed. PACS 78.35.+c; 77.84.-s; 61.82.Rx     

Practical aspects associated with location planning for maternal and perinatal assistance in Brazil

A study has been carried out aimed at reducing perinatal mortality in the municipality of Rio de Janeiro through a better distribution of health care facilities. The algorithmic aspects are detailed elsewhere and here the emphasis is on practical issues and difficulties encountered. A 3-level hierarchical model was developed. Both uncapacitated and capacitated versions are briefly described together with some results based on actual data. The project brought to light many contradictions between OR theory and practice in developing countries and, unfortunately, the models developed were not implemented by the municipality health authorities. Possible reasons for this outcome are analysed.     

Mercury removal from aqueous solution and flue gas by adsorption on activated carbon fibres

The use of two activated carbon fibres, one laboratorial sample prepared from a commercial acrylic textile fibre and one commercial sample of Kynol^®, as prepared/received and modified by reaction with powdered sulfur and H₂S gas in order to increase the sulfur content were studied for the removal of mercury from aqueous solution and from flue gases from a fluidized bed combustor. The sulfur introduced ranged from 1 to 6 wt.% depending on the method used. The most important parameter for the mercury uptake is the type of sulfur introduced rather than the total amount and it was found that the H₂S treatment of ACF leads to samples with the highest mercury uptake, despite the lower sulfur amount introduced. The modified samples by both methods can remove HgCl₂ from aqueous solutions at pH 6 within the range 290-710 mg/g (ACF) which can be favourably compared with other studies already published. The use of a filter made with an activated carbon fibre modified by powdered sulfur totally removed the mercury species present in the flue gases produced by combustion of fossil fuel.     

An Introduction to Constant Curvature Spaces in the Commutative (Segre) Quaternion Geometry

It is known that complex numbers can be associated with plane Euclidean geometry and their functions are successfully used for studying extensions of Euclidean geometry, i.e., non-Euclidean geometries and surfaces differential geometry. In this paper we begin to study the constant curvature spaces associated with the geometry generated by commutative elliptic-quaternions and we show how the “mathematics” they generate allows us to introduce these spaces and obtain the geodesic equations without developing a complete mathematical apparatus as the one developed for Riemannian geometry.     

On a recursive method for the estimation of unknown parameters of partially observed chaotic systems

We investigate a recently proposed method for on-line parameter estimation and synchronization in chaotic systems. This novel technique has been shown effective to estimate a single unknown parameter of a primary chaotic system with known functional form that is only partially observed through a scalar time series. It works by periodically updating the parameter of interest in a secondary system, with the same functional form as the primary one but no explicit coupling between their dynamic variables, in order to minimize a suitably defined cost function. In this paper, we review the basics of the method, and investigate its robustness and new extensions. In particular, we study the performance of the novel technique in the presence of noise (either observational, i.e., an additive contamination of the observed time series, or dynamical, i.e., a random perturbation of the system dynamics) and when there is a mismatch between the primary and secondary systems. Numerical results, including comparisons with other techniques, are presented. Finally, we investigate the extension of the original method to perform the estimation of two unknown parameters and illustrate its effectiveness by means of computer simulations.